KR100969675B1 - Novel organic dye containing n-arylcarbazole moiety and preparation thereof - Google Patents

Abstract

The present invention relates to a novel N-arylcarbazole moiety-containing organic dye and a method for preparing the same, in which fluorene and carbazole are used as electron donors, thiophene units at intermediate linkages, and cyanoacrylic acid or rhoda as electron acceptors. The dye compound of the present invention having nin-3-acetic acid is used in dye-sensitized solar cells (DSSC) to improve the molar absorption coefficient, J _sc (single-circuit photocurrent density) and photoelectric conversion efficiency over conventional dyes. The efficiency of the solar cell can be greatly improved, and purification can be performed without using an expensive column, thereby significantly lowering the cost of dye synthesis.

Solar cell, dye-sensitized, dye, photoelectric conversion element

Description

Novel N-arylcarbazole residue-containing organic dyes and preparation methods therefor {NOVEL ORGANIC DYE CONTAINING N-ARYLCARBAZOLE MOIETY AND PREPARATION THEREOF}

1 (a) to 1 (f) show absorbance and emission spectra in ethanol of the dye compounds 1a-1, 1a-2, 1b-1, 1b-2, 1c and 1d, respectively, and the TiO ₂ layer of the present invention, respectively. Absorption spectrum when supported on the phase,

2 (a) to 2 (f) respectively show the geometry (HOMO and LUMO molecular orbitals, B3LYP / 3) of the dye compounds 1a-1, 1a-2, 1b-1, 1b-2, 1c and 1d of the present invention, respectively. Is a schematic diagram (calculated by TD-DFT for -21G),

3 is an incident photon-to-current conversion efficiency (IPCE) spectrum of a solar cell prepared using the dye compounds 1a-1, 1a-2, 1b-1, 1b-2, 1c, and 1d of the present invention.

The present invention relates to novel organic dyes containing N-arylcarbazole moieties for use in dye-sensitized solar cells (DSSCs) and methods for their preparation.

Since the development of the dye-sensitized nanoparticle titanium oxide solar cell by the team of Michael Gratzel of the Swiss National Lausanne Institute of Advanced Technology (EPFL) in 1991, much work has been done in this area. Dye-sensitized solar cells have the potential to replace conventional amorphous silicon solar cells because of their higher efficiency and lower manufacturing costs than conventional silicon-based solar cells. It is a photoelectrochemical solar cell whose main constituent material is a dye molecule capable of absorbing and generating electron-hole pairs, and a transition metal oxide for transferring generated electrons.

As a dye used in dye-sensitized solar cells, ruthenium metal complexes having high photovoltaic conversion efficiency have been widely used, but this ruthenium metal complex has a disadvantage of being too expensive.

Recently, metal-free organic dyes, which exhibit excellent physical properties in terms of absorption efficiency, redox reaction stability, and intermolecular charge-transfer (CT) -based absorption, can replace expensive ruthenium metal complexes. It has been found that it can be used as a dye for solar cells, and research on organic dyes lacking metals has been focused on.

Organic dyes generally have a structure of electron donor-electron acceptor residues linked by π-binding units. In most organic dyes, amine derivatives act as electron donors, 2-cyanoacrylic acid or rhodanine residues act as electron acceptors, and these two sites are π-bonds such as metaine units or thiophene chains. Connected by the system.

In general, the structural change of the amine unit, which is an electron donor, results in a change in the electronic properties, for example, an absorption spectrum shifted toward blue, and by changing the π-bond length, the absorption spectrum and redox potential. Can be adjusted.

However, most of the organic dyes known to date show low conversion efficiency and low driving stability compared to ruthenium metal complex dyes, which are found to be due to the aggregation of dyes on the semiconductor surface and the formation of unstable radical species during the redox reaction cycle. lost.

Therefore, by changing the type or the π-bond length of the electron donor and acceptor, efforts to develop a new dye having an improved molar absorption coefficient and high photoelectric conversion efficiency compared to the existing organic dye compounds continue.

Accordingly, an object of the present invention is to provide an organic dye and a method for manufacturing the same, which can improve the efficiency of a solar cell by exhibiting an improved molar absorption coefficient and photoelectric conversion efficiency than conventional metal complex dyes.

In addition, the present invention exhibits a markedly improved photoelectric conversion efficiency including the dye, a dye-sensitized photoelectric conversion device excellent in J _sc (short circuit photocurrent density) and a molar absorption coefficient, and the solar efficiency is significantly improved It is an object to provide a battery.

In order to achieve the above object, the present invention provides an N-arylcarbazole-based dye represented by the following formula (1).

Where

X is 9,9-dimethylfluorenyl or 4- (2,2-diphenylvinyl) phenyl,

Y is a cyanoacrylic acid residue or a rhodanine-3-acetic acid residue,

n is an integer from 1 to 5, optionally two or more thiophene units may be linked to a vinyl group.

Also,

(1) 3-iodocarbazole is subjected to still coupling reaction with a compound of Formula 2 to prepare a compound of Formula 3,

(2) preparing a compound of formula 4 by reacting a compound of formula 3 with 2-iodo-9,9-dimethylfluorene and Ullmann;

(3) preparing a compound of formula 5 by lithiation of the compound of formula 4 with n-butyllithium and subsequently cooling with dimethylformamide (DMF);

(3) reacting the compound of formula 5 with cyanoacetic acid in the presence of piperidine in CH ₃ CN or reacting the compound of formula 5 with rhodanine-3-acetic acid and ammonium acetate in acetic acid

It provides a method for producing a dye represented by the formula (1a) or 1b.

Wherein n is an integer from 1 to 5, optionally two or more thiophene units may be linked to a vinyl group.

Also,

(1) 3-iodocarbazole is subjected to still coupling reaction with a compound of Formula 2 to prepare a compound of Formula 3,

(2) a compound of Chemical Formula 3 is prepared by coupling a compound of Chemical Formula 3 with 1- (2- (4-bromophenyl) -1-phenylvinyl) benzene and Ullmann;

(3) formally compounding the compound of formula 6 with n-butyllithium to prepare a compound of formula 7,

(3) reacting the compound of formula 7 with cyanoacetic acid in the presence of piperidine in CH ₃ CN

It provides a method for producing a dye represented by the formula (1c).

[Formula 2]

(3)

Wherein n is 1.

Also,

(1) 3-iodocarbazole is subjected to still coupling reaction with a compound of Formula 2 to prepare a compound of Formula 3,

(2) preparing a compound of formula 4 by reacting a compound of formula 3 with 2-iodo-9,9-dimethylfluorene and Ullmann;

(3) Lithium-substituted compound of Formula 4 with n-butyllithium and subsequently cooled with dimethylformamide to prepare a compound of Formula 5

(4) A compound of formula 8 is prepared by coupling a compound of formula 5 with (2-thienylmethyl) triphenylphosphinium bromide and Honor-Emmons-Wittig.

(5) preparing a compound of formula 9 by formylating a compound of formula 8 with n-butyllithium,

(6) reacting a compound of formula 9 with cyanoacetic acid in the presence of piperidine in CH ₃ CN

It provides a method for producing a dye represented by the following formula (1d).

[Formula 2]

(3)

[Formula 4]

[Chemical Formula 5]

Wherein n is 1.

In another aspect, the present invention provides a dye-sensitized photoelectric conversion device comprising an oxide semiconductor fine particle carrying a compound represented by the formula (1).

In another aspect, the present invention provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion device.

Hereinafter, the present invention will be described in detail.

The present inventors use fluorene and carbazole as electron donors, introduce thiophene units to increase the molar extinction coefficient and increase the stability of the device at the intermediate connection portion, and are well connected to the TiO ₂ reforming so that the electron transport ability When preparing a dye-sensitized solar cell by supporting a compound represented by the formula (1) having a new organic dye structure on the oxide semiconductor fine particles using the best cyanoacrylic acid or rhodanine-3-acetic acid as an electron acceptor, The J _sc (single circuit photocurrent density) and the molar extinction coefficient have been confirmed to show better efficiency than the conventional dye-sensitized solar cell, thereby completing the present invention.

N-arylcarbazole-based organic dye of the present invention is characterized by represented by the formula (1), preferably has a structure of the formula (1a-1, 1a-2, 1b-1, 1b-2, 1c or 1d) .

[Formula 1]

[Formula 1c]

≪ RTI ID = 0.0 &

Wherein X, Y and n are as defined above.

The present invention also provides a dye represented by the formula 1a or 1b, a dye represented by the formula (1c) and a dye represented by the formula (1d) of the dye represented by the formula (1),

"Stille coupling" reaction means reacting according to still reaction conditions using tetrakis (triphenylphosphine) palladium (0), dimethylformamide and stanylthiophene; "Ullmann coupling" reaction means reacting according to the Ulman reaction conditions using copper bronze, potassium carbonate and 18-crown-6; "Honor-Emons-Witig coupling" reaction means to react according to the Honor-Emons-Witig reaction conditions using potassium- tert -butoxide in tetrahydrofuran.

Preferably, the dyes 1a and 1b of the present invention may be prepared according to Scheme 1 below.

Preferably, the dyes 1c and 1d of the present invention may be prepared according to Scheme 2 below.

In the above scheme, 3-iodocarbazole used as starting material in the preparation of the dye of formula 1 can be obtained by conventional methods.

In addition, the present invention provides a dye-sensitized photoelectric conversion device, the dye-sensitized photoelectric conversion device is characterized in that the dye represented by the formula (1) on the oxide semiconductor fine particles. The present invention is a dye-sensitized photoelectric conversion device in addition to using the dye represented by the formula (1) can be applied to the method of manufacturing a dye-sensitized photoelectric conversion device for solar cells using a conventional dye, of course, preferably the present invention The dye-sensitized photoelectric conversion device may be prepared by fabricating a thin film of an oxide semiconductor on a substrate using oxide semiconductor fine particles, and then supporting the dye of the present invention on the thin film.

In this invention, it is preferable that the surface is electroconductive as a board | substrate which provides the thin film of an oxide semiconductor, and what is marketed can also be used. As a specific example, conductive metal oxides such as tin oxide coated with indium, fluorine, and antimony on a surface of glass or a transparent polymer material such as polyethylene terephthalate or polyethersulfone, or a metal thin film such as steel, silver, or gold may be used. The formed thing can be used. In this case, the conductivity is preferably 1000 Ω or less, particularly preferably 100 Ω or less.

As the fine particles of the oxide semiconductor, a metal oxide is preferable. As specific examples, oxides such as titanium, tin, zinc, tungsten, zirconium, gallium, indium, yttrium, niobium, tantalum and vanadium can be used. Of these, oxides such as titanium, tin, zinc, niobium and indium are preferable, among these, titanium oxide, zinc oxide and tin oxide are more preferable, and titanium oxide is most preferred. The oxide semiconductor may be used alone, or may be mixed or coated on the surface of the semiconductor.

The particle diameter of the fine particles of the oxide semiconductor is preferably 1 to 500 nm, more preferably 1 to 100 nm as the average particle diameter. In addition, the fine particles of the oxide semiconductor may be mixed with a large particle size and a small particle size, or may be used as a multilayer.

The oxide semiconductor thin film is a method of forming oxide semiconductor fine particles into a thin film directly on a substrate by spray spraying, a method of electrically depositing a semiconductor fine particle thin film using a substrate as an electrode, a slurry of semiconductor fine particles or semiconductor fine particles such as a semiconductor alkoxide. After applying the paste containing the fine particles obtained by hydrolyzing the precursor onto the substrate, it can be produced by a method of drying, curing or baking, and a method of applying the paste onto the substrate is preferred. In the case of this method, a slurry can be obtained by disperse | distributing the oxide semiconductor microparticles | fine-particles which are secondary aggregated so that an average primary particle diameter may be 1-200 nm in a dispersion medium by a conventional method.

The dispersion medium for dispersing the slurry can be used without particular limitation so long as it can disperse the semiconductor fine particles, and alcohols such as water and ethanol, ketones such as acetone and acetylacetone, or hydrocarbons such as hexane can be used, and these can be mixed and used. Among them, it is preferable to use water among them in order to reduce the viscosity change of the slurry. Moreover, a dispersion stabilizer can be used for the purpose of stabilizing the dispersion state of oxide semiconductor microparticles | fine-particles. Specific examples of the dispersion stabilizer that can be used include acids such as acetic acid, hydrochloric acid and nitric acid, or acetylacetone, acrylic acid, polyethylene glycol, and polyvinyl alcohol.

The substrate coated with the slurry can be fired, and its firing temperature is at least 100 ° C, preferably at least 200 ° C, and the upper limit is generally below the melting point (softening point) of the substrate, and usually the upper limit is 900 ° C, preferably 600. It is below ℃. In the present invention, the firing time is not particularly limited, but is generally within 4 hours.

It is preferable that the thickness of the thin film on a board | substrate in this invention is 1-200 micrometers, Preferably it is 1-50 micrometers. Although some thin layers of oxide semiconductor fine particles are welded when firing, such welding is not particularly troubled for the present invention.

In addition, the oxide semiconductor thin film may be subjected to secondary treatment. For example, the performance of a semiconductor thin film may be improved by directly depositing a thin film for each substrate and drying or refiring it in a solution such as an alkoxide, chloride, nitride, or sulfide of the same metal as the semiconductor. Examples of the metal alkoxide include titanium ethoxide, titanium isopropyl epoxide, titanium t-butoxide, n-dibutyl-diacetyl tin and the like, and an alcohol solution thereof can be used. As a chloride, titanium tetrachloride, tin tetrachloride, zinc chloride, etc. are mentioned, for example, The aqueous solution can be used. The oxide semiconductor thin film thus obtained is composed of fine particles of an oxide semiconductor.

In addition, the method of supporting the dye on the oxide semiconductor fine particles formed in the thin film phase in the present invention is not particularly limited, as a specific example, a solution obtained by dissolving the dye represented by the formula (1) in a solvent capable of dissolving, or disperse the dye The method of immersing the board | substrate with which the said oxide semiconductor thin film was installed in the dispersion liquid obtained by this is mentioned. The concentration in the solution or dispersion can be appropriately determined by the dye. The deposition time is usually from room temperature to the boiling point of the solvent, and the deposition time is about 1 minute to 48 hours. Specific examples of the solvent that can be used to dissolve the dye include methanol, ethanol, acetonitrile, dimethyl sulfoxide, dimethylformamide, acetone, t-butanol and the like. The dye concentration of the solution is usually 1 x 10 ^-6 M to 1 M is suitable, preferably 1 x 10 ^-5 M to 1 x 10 ^-1 M. In this way, the photoelectric conversion element of this invention which has oxide semiconductor microparticles | fine-particles on the thin film sensitized with dye can be obtained.

The dye represented by the formula (1) supported by the present invention may be one kind or may be mixed in several kinds. In addition, when mixing, another dye or a metal complex dye can be mixed with the dye of this invention. Examples of the metal complex dyes that can be mixed are not particularly limited, but ruthenium complexes, quaternary salts thereof, phthalocyanine, porphyrin, and the like are preferable, and organic dyes used for mixing include metal-free phthalocyanine, porphyrin, cyanine, merocyanine, Methine dyes such as oxonol, triphenylmethane, and acrylic acid dyes as shown in WO2002 / 011213, and dyes such as xanthene, azo, anthraquinone and perylene-based dyes (MK Nazeeruddin, A). .Kay, I.Rodicio, R.Humphry-Baker, E.Muller, P.Liska, N.Vlachopoulos, M.Gratzel, J. Am. Chem. Soc., Vol. 115, p . 6382 (1993). ). When using two or more types of dyes, the dyes may be adsorbed onto the semiconductor thin film in sequence, or may be mixed and dissolved to adsorb them.

In the present invention, when the dye is supported on the thin film of the oxide semiconductor fine particles, it is preferable to support the dye in the presence of the inclusion compound in order to prevent the dyes from bonding. Examples of the inclusion compound include carboxylic acids such as deoxycholic acid, dehydrodeoxycholic acid, kenodeoxycholic acid, methyl ester of cholate, and sodium cholate, steroidal compounds such as polyethylene oxide and cholic acid, crown ether, cyclodextrin, and calix arene, Polyethylene oxide and the like can be used.

After the dye is supported, the semiconductor electrode surface can be treated with an amine compound such as 4-t-butyl pyridine or a compound having an acidic group such as acetic acid or propionic acid. As a treatment method, for example, a method of dipping a substrate provided with a thin film of semiconductor fine particles in which a dye is supported in an amine ethanol solution may be used.

In another aspect, the present invention provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion device, using a dye-sensitized photoelectric conversion device using the oxide semiconductor fine particles carrying the dye represented by the formula (1) In addition, conventional methods for manufacturing a solar cell using a conventional photoelectric conversion device may be applied, and, as a specific example, a photoelectric conversion device electrode (cathode) and a counter electrode supporting the dye represented by Formula 1 on the oxide semiconductor fine particles. (Anode), a redox electrolyte, a hole transport material, a p-type semiconductor, or the like.

Preferably, one example of a specific method of manufacturing a dye-sensitized solar cell of the present invention is the step of coating a titanium oxide paste on a conductive transparent substrate, baking the substrate coated with a paste to form a titanium oxide thin film, titanium oxide thin film Impregnating the formed substrate into a mixed solution in which the dye represented by Chemical Formula 1 is dissolved to form a titanium oxide film electrode on which the dye is adsorbed, and providing a second glass substrate having a counter electrode formed thereon. Forming a hole penetrating a glass substrate and a counter electrode, placing a thermoplastic polymer film between the counter electrode and the dye-adsorbed titanium oxide film electrode, and performing a heat compression process to perform the counter electrode and titanium oxide. Bonding a film electrode to the thermoplastic polymer film between the counter electrode and the titanium oxide film electrode through the hole; Implanting be and can be prepared through the step of sealing the thermoplastic polymer.

Redox electrolytes, hole transport materials, p-type semiconductors, and the like may be in the form of liquids, coagulants (gels and gels), solids, and the like. As liquids, redox electrolytes, dissolved salts, hole transport materials, p-type semiconductors, and the like are dissolved in a solvent, and at room temperature, dissolved salts, etc., in the case of coagulation bodies (gels and gels), these are polymer matrices or low molecular gelling agents. What was contained in etc. can be mentioned, respectively. As the solid, a redox electrolyte, a dissolved salt, a hole transport material, a p-type semiconductor, or the like can be used.

Examples of the hole transport material include an amine derivative, a conductive polymer such as polyacetylene, polyaniline, and polythiophene, and an object using a discotech liquid crystal phase such as triphenylene-based compound. Moreover, CuI, CuSCN, etc. can be used as a p-type semiconductor. It is preferable that the counter electrode has conductivity and catalyzes the reduction reaction of the redox electrolyte. For example, platinum, carbon, rhodium, ruthenium, or the like deposited on glass or a polymer film, or coated with conductive fine particles can be used.

As the redox electrolyte used in the solar cell of the present invention, a halogen redox electrolyte composed of a halogen compound having a halogen ion as a large ion and a halogen molecule, a ferrocyanate-ferrocyanate, a ferrocene-ferricinium ion, a cobalt complex and the like Metal redox-based electrolytes such as metal complexes, organic redox-based electrolytes such as alkylthiol-alkyldisulfides, viologen dyes, and hydroquinone-quinones, and the like, and halogen redox-based electrolytes are preferable. As a halogen molecule in the halogen redox electrolyte composed of halogen compound-halogen molecules, an iodine molecule is preferable. As a halogen compound having a halogen ion as a large ion, halogenated metal salts such as LiI, NaI, KI, CaI ₂ , MgI ₂ and CuI, or organic ammonium salts of halogens such as tetraalkylammonium iodine, imidazolium iodine and pyridium iodine, Or I ₂ can be used.

In addition, when the redox electrolyte is configured in the form of a solution containing the same, an electrochemically inert one may be used as the solvent. Specific examples include acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxy propionitrile, methoxy acetonitrile, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, butyrolactone, dimethoxyethane, dimethyl carbonate, 1,3-dioxolane, methylformate, 2-methyltetrahydrofuran, 3-methoxy-oxazolidin-2-one, sulfolane, tetrahydrofuran, water, and the like, in particular acetonitrile, Propylene carbonate, ethylene carbonate, 3-methoxy propionitrile, ethylene glycol, 3-methoxy-oxazolidin-2-one, butyrolactone and the like are preferable. The solvents may be used alone or in combination. In the case of a gel positive electrolyte, one containing an electrolyte or an electrolyte solution in a matrix such as an oligomer and a polymer, or one containing an electrolyte or an electrolyte solution in the same manner as a starch gelling agent can be used. The concentration of the redox electrolyte is preferably 0.01 to 99% by weight, more preferably 0.1 to 30% by weight.

In the solar cell of the present invention, a counter electrode (anode) is disposed in a photoelectric conversion element (cathode) on which a dye is carried on an oxide semiconductor fine particle on a substrate so as to face it, and a solution containing a redox electrolyte is filled therebetween. Can be obtained.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

[Example]

Example 1 Synthesis of Dye

All reactions were run under argon gas and the solvent was distilled off with a suitable reagent purchased from Sigma-Adrich. 1H and 13C NMR spectra were measured with a Varian Mercury 300 spectrometer, elemental analysis with a Carlo Elba Instruments CHNS-O EA 1108 analyzer, and mass spectra with a JEOL JMS-SX102A instrument. Absorption and emission spectra were measured with a Perkin-Elmer Lambda 2S UV-visible spectrometer and a Perkin LS fluorescence spectrometer, respectively.

<Circulating Voltammetry> BAS 100B (Bioanalytical Systems, Inc.) was used as a cyclic voltammeter. A three-electrode system consisting of gold disks, working electrodes and platinum wire electrodes was used. The redox potential of the dye on TiO ₂ was measured in CH ₃ CN using 0.1 M ( n- C ₄ H ₉ ) ₄ N-PF ₆ at a scan rate of 50 mV s ⁻¹ (vs. Fc / Fc ⁺ ). .

I) 3- (thiophen-2-yl) carbazole (Compound 3, n = 1)

3-iodocarbazole (1.0 g, 3.41 mmol), tributyl (thiophen-2-yl) stanan (1.27 g, 3.41 mmol) and Pd (PPh ₃ ) ₄ (0.197 g, 0.17 mmol) were dimethylform It was stirred and heated at 100 ° C. for 12 hours in amide (30 ml). After cooling the mixed solution, water (50 ml) was added to the mixed solution, and the mixture was extracted with dichloromethane (50 × 5). The organic layer was separated and dried over magnesium sulfate. After removing the solvent under vacuum, the obtained solid was subjected to silica gel chromatography (developing agent MC: Hx = 1: 2, R _f = 0.4) to obtain the title compound as a white solid (yield 82%).

Mp: 197 ° C. 1 H NMR (acetone-d ₆ ): δ 10.45 (br, 1H), 8.43 (s, 1H), 8.20 (d, 1H, J = 8.1 Hz), 7.72 (d, 1H, J = 8.1 Hz), 7.55 ( d, 1H, J = 8.1 Hz), 7.53 (d, 1H, J = 8.1 Hz), 7.44 (d, 1H, J = 3.6 Hz), 7.41 (t, 1H, J = 8.1 Hz), 7.38 (d, 1H, J = 5.1 Hz), 7.21 (t, 1H, J = 8.1 Hz), 7.12 (dd, 1H, J = 3.6, 5.1 Hz). 13C {1H} NMR (CDCl ₃ / acetone-d ₆ ): δ 145.8, 140.4, 139.4, 127.8, 125.9, 125.8, 124.2, 123.6, 123.0, 121.9, 120.2, 119.6, 119.1, 117.5, 111.1, 110.9. MS: m / z 249 [M &lt; + &gt;]. Anal. Calcd for C ₁₆ H ₁₁ NS: C, 77.07; H, 4.45. Found: C, 76.88; H, 4.28.

II) 3- (5- (thiophen-2-yl) thiophen-2-yl) carbazole (Compound 3, n = 2)

The same process as in step I) was carried out to obtain the title compound as a white solid (yield 78%).

Mp: 201 ° C. 1 H NMR (acetone-d ₆ ): δ 10.47 (br, 1H), 8.46 (s, 1H), 8.23 (d, 1H, J = 7.2 Hz), 7.74 (d, 1H, J = 8.1 Hz), 7.59 ( d, 1H, J = 7.2 Hz), 7.54 (d, 1H, J = 8.1 Hz), 7.43 (d, 1H, J = 3.6 Hz), 7.42 (t, 1H, J = 7.5 Hz), 7.41 (d, 1H, J = 3.6 Hz), 7.32 (d, 1H, J = 5.1 Hz), 7.27 (d, 1H, J = 3.6 Hz), 7.22 (t, 1H, J = 7.5 Hz), 7.10 (dd, 1H, J = 5.1, 3.6 Hz). 13C {1H} NMR (acetone-d ₆ ): δ 145.6, 141.6, 140.7, 138.3, 135.9, 128.9, 126.9, 126.1, 125.7, 125.3, 124.6, 124.2, 123.8, 123.7, 121.3, 120.9, 118.4, 118.0, 112.3 , 112.0. MS: m / z 359 [M &lt; + &gt;]. Anal. Calcd for C ₂₀ H ₁₃ NS ₂ : C, 72.47; H, 3.95. Found: C, 72.18; H, 3.85.

III) 9- (9,9-dimethylfluoren-2-yl) -3- (thiophen-2-yl) -carbazole (compound 4, n = 1)

Compound 3 (n = 1) (1.40 g, 5.61 mmol) prepared in step I), 2-iodo-9,9-dimethylfluorene (1.97 g, 6.17 mmol), anhydrous potassium carbonate powder (1.55 g, 11.22 mmol), copper bronze (0.36 g, 5.61 mmol) and 18-crown-6 (0.22 g, 0.84 mmol) were refluxed in 1,2-dichlorobenzene (50 ml) for 48 hours. After cooling the reaction solution, an insoluble inorganic substance was filtered under suction and a dark brown filtrate was recovered. Insoluble matter was washed with dichloromethane (3 × 30 mL). The combined filtrate and organic phase were washed with dilute aqueous ammonia and water and dried over magnesium sulfate. After the solvent was removed under reduced pressure, the obtained solid was subjected to silica gel chromatography (developing agent MC: Hx = 1: 3, R _f = 0.4) to obtain the title compound (1.96 g) (yield 79%).

Mp: 207 ° C. 1 H NMR (CDCl ₃ ): δ 8.39 (s, 1H), 8.21 (d, 1H, J = 7.5 Hz), 7.94 (d, 1H, J = 8.1 Hz), 7.82 (s, 1H, J = 8.1 Hz) , 7.71 (d, 1H, J = 8.4 Hz), 7.64 (s, 1H), 7.55 (d, 1H, J = 8.1 Hz), 7.50 (t, 1H, J = 7.5 Hz), 7.48 (d, 1H, J = 8.4 Hz), 7.46 (d, 1H, J = 8.1 Hz), 7.42 (d, 1H, J = 8.1 Hz), 7.41 (t, 1H, J = 7.5 Hz), 7.39 (t, 1H, J = 7.5 Hz), 7.38 (d, 1H, J = 3.6 Hz), 7.33 (t, 1H, J = 7.5 Hz), 7.28 (d, 1H, J = 5.1 Hz), 7.13 (dd, 1H, J = 5.1, 3.6 Hz), 1.58 (s, 6 H). 13C {1H} NMR (CDCl ₃ ): δ 155.6, 153.9, 145.7, 141.6, 140.7, 138.7, 138.5, 136.5, 131.2, 130.9, 130.0, 128.1, 127.8, 127.4, 126.9, 126.4, 126.9, 124.7, 123.9, 123.4 , 122.9, 122.4, 121.5, 121.3, 120.6, 120.3, 117.9, 110.3, 47.3, 27.3. MS: m / z 441 [M &lt; + &gt;]. Anal. Calcd for C ₃₁ H ₂₃ NS: C, 84.32; H, 5.25. Found: C, 84.04; H, 5.14.

IV) 9- (9,9-dimethylfluoren-2-yl) -3- (5- (thiophen-2-yl) -thiophen-2yl) carbazole (compound 4, n = 2)

The same process as in step III) was carried out to obtain the title compound as a white solid (yield 76%).

Mp: 211 ° C. 1 H NMR (CDCl ₃ ): δ 8.38 (s, 1H), 8.21 (d, 1H, J = 7.5 Hz), 7.94 (d, 1H, J = 8.1 Hz), 7.81 (d, 1H, J = 8.1 Hz) , 7.69 (d, 1H, J = 8.7 Hz), 7.63 (s, 1H), 7.54 (d, 1H, J = 8.1 Hz), 7.52 (t, 1H, J = 7.5 Hz), 7.48 (d, 1H, J = 8.4 Hz), 7.45 (d, 1H, J = 8.7 Hz), 7.41 (t, 1H, J = 7.5 Hz), 7.39 (t, 1H, J = 7.5 Hz), 7.35 (d, 1H, J = 8.4 Hz), 7.33 (t, 1H, J = 7.5 Hz), 7.28 (d, 1H, J = 3.9 Hz), 7.23 (d, 1H, J = 3.9 Hz), 7.22 (d, 1H, J = 5.1 Hz ), 7.20 (d, 1H, J = 3.6 Hz), 7.05 (dd, 1H, J = 3.6, 5.1 Hz), 1.57 (s, 6H). 13C {1H} NMR (CDCl ₃ ): δ 155.6, 153.9, 144.6, 141.7, 140.7, 138.8, 138.5, 137.9, 136.5, 135.8, 127.9, 127.8, 127.4, 126.5, 125.9, 124.8, 124.4, 124.2, 124.1, 124.0 , 123.5, 123.4, 122.9, 122.8, 121.5, 121.3, 120.7, 120.4, 120.3, 117.6, 110.4, 110.2, 47.3, 27.3. MS: m / z 523 [M &lt; + &gt;]. Anal. Calcd for C ₃₅ H ₂₅ NS ₂ : C, 80.27; H, 4.81. Found: C, 79.96; H, 4.73.

V) 9- (9,9-dimethylfluoren-2-yl) carbazol-6-yl) -thiophen-2-carboaldehyde (Compound 5, n = 1)

Compound 4 (n = 1) (0.26 g, 0.59 mmol) prepared in step III) was dissolved in tetrahydrofuran (20 mL) and cooled to −78 ° C. under N ₂ . To this was added n-butyllithium (0.92 mL, 1.6 M solution in hexane, 1.47 mmol) dropwise over 10 minutes with vigorous stirring. The temperature of the solution was brought to 0 ° C. for 1 hour and then left at this temperature for an additional hour. The solution was cooled back to −78 ° C. and anhydrous dimethylformamide (1 mL) was added directly. The resulting solution was allowed to come to room temperature and stirred overnight. HCl (1 mL) diluted in 20 mL water was added to the reaction solution to complete the reaction, followed by extraction with diethyl ether (3 × 20 mL). The combined organic extracts were dried over anhydrous magnesium sulfate and filtered. The filtrate was purified by silica gel chromatography (developing agent MC: Hx = 1: 2, R _f = 0.3) to give the title compound (yield 89%).

Mp: 226 ° C. 1 H NMR (CDCl ₃ ): δ 9.95 (s, 1H), 8.74 (s, 1H), 8.38 (d, 1H, J = 7.5 Hz), 8.14 (d, 1H, J = 7.5 Hz), 7.99 (d, 1H, J = 3.9 Hz), 7.96 (d, 1H, J = 8.1 Hz), 7.90 (d, 1H, J = 8.4 Hz), 7.86 (s, 1H), 7.74 (d, 1H, J = 4.5 Hz) , 7.64 (d, 1H, J = 8.1 Hz), 7.63 (t, 1H, J = 7.5 Hz), 7.55 (d, 1H, J = 8.4 Hz), 7.49 (t, 1H, J = 7.5 Hz), 7.43 (d, 1H, J = 6.9 Hz), 7.42 (t, 1H, J = 7.5 Hz), 7.38 (d, 1H, J = 6.9 Hz), 7.35 (t, 1H, J = 7.5 Hz), 1.61 (s , 6H). 13C {1H} NMR (CDCl ₃ ): δ 182.7, 156.1, 155.7, 153.9, 141.8, 141.7, 141.6, 139.1, 138.4, 137.9, 136.1, 127.9, 127.4, 126.9, 125.9, 125.3, 124.8, 124.1, 123.2, 123.0 , 122.9, 121.4, 121.3, 120.7, 120.6, 120.4, 118.6, 110.6, 110.4, 47.3, 27.2. MS: m / z 469 [M &lt; + &gt;]. Anal. Calcd for C ₃₂ H ₂₃ NOS: C, 81.85; H, 4.94. Found: C, 81.58; H, 4.79.

VI) 5- (5- (9- (9,9-dimethylfluoren-2-yl) carbazol-6-yl) -thiophen-2-yl) thiophene-2-carbaldehyde (Compound 5, n = 2)

The same process as in step V) was carried out to obtain the title compound as a yellow solid (yield 86%).

Mp: 234 ° C. 1 H NMR (CDCl ₃ ): δ 9.84 (s, 1H), 8.37 (s, 1H), 8.21 (d, 1H, J = 7.8 Hz), 7.92 (d, 1H, J = 8.1 Hz), 7.81 (d, 1H, J = 8.1 Hz), 7.66 (d, 1H, J = 8.4 Hz), 7.63 (d, 1H, J = 3.9 Hz), 7.62 (s, 1H), 7.51 (d, 1H, J = 8.1 Hz) , 7.50 (t, 1H, J = 7.5 Hz), 7.47 (d, 1H, J = 8.1 Hz), 7.46 (t, 1H, J = 7.5 Hz), 7.42 (d, 1H, J = 8.4 Hz), 7.41 (t, 1H, J = 7.5 Hz), 7.36 (d, 1H, J = 8.1 Hz), 7.34 (t, 1H, J = 7.5 Hz), 7.34 (d, 1H, J = 3.6 Hz), 7.29 (d , 1H, J = 3.6 Hz), 7.23 (d, 1H, J = 3.9 Hz), 1.58 (s, 6H). 13C {1H} NMR (CDCl ₃ ): δ 182.5, 155.6, 153.9, 147.7, 141.7, 141.2, 141.0, 138.9, 138.4, 137.7, 136.2, 134.0, 127.8, 127.4, 127.3, 126.7, 125.8, 125.7, 124.3, 124.0 , 123.9, 123.7, 123.3, 123.2, 122.9, 121.4, 121.3, 120.6, 120.5, 120.3, 117.8, 110.5, 110.3, 47.3, 27.2. MS: m / z 551 [M &lt; + &gt;]. Anal. Calcd for C ₃₆ H ₂₅ NOS ₂ : C, 78.27; H, 4.57. Found: C, 78.01; H, 4.51.

VII) 2-cyano-3- (5- (9- (9,9-dimethylfluoren-2-yl) carbazol-6-yl) thiophen-2-yl) acrylic acid (Compound 1a-1)

The mixture of compound 5 (n = 1) (0.3 g, 0.64 mmol) and cyanoacetic acid (0.082 g, 0.96 mmol) prepared in step V) was vacuum dried, and then acetonitrile (20 mL) and piperidine (0.063 mL). ) And the mixed solution was refluxed for 6 hours. The reaction solution was cooled, the organic layer was removed under vacuum, and the obtained solid was subjected to silica gel chromatography (developing agent EA: MeOH = 10: 1, R _f = 0.2) to obtain the title compound (0.19 g) (yield 89%).

Mp: 251 ° C. _{1H NMR (DMSO- d 6):} δ 8.77 (s, 1H), 8.49 (s, 1H), 8.43 (d, 1H, J = 7.8 Hz), 8.13 (d, 1H, J = 8.1 Hz), 8.04 ( d, 1H, J = 3.9 Hz), 7.96 (d, 1H, J = 8.1 Hz), 7.90 (s, 1H), 7.89 (d, 1H, J = 8.7 Hz), 7.84 (d, 1H, J = 3.9 Hz), 7.62 (d, 1H, J = 8.1 Hz), 7.61 (d, 1H, J = 7.8 Hz), 7.52 (t, 1H, J = 7.5 Hz), 7.51 (d, 1H, J = 8.7 Hz) , 7.47 (t, 1H, J = 7.5 Hz), 7.41 (t, 1H, J = 7.8 Hz), 7.40 (d, 1H, J = 8.7 Hz), 7.36 (t, 1H, J = 7.5 Hz), 1.54 (s, 6H). 13C {1H} NMR (DMSO- d 6): δ 163.8, 155.4, 154.5, 153.7, 146.5, 141.6, 141.0, 138.3, 137.7, 135.3, 134.1, 133.7, 127.8, 127.3, 127.1, 125.6, 125.1, 124.6, 124.1 , 123.5, 122.9, 122.5, 121.6, 121.4, 121.2, 120.6, 120.5, 119.1, 118.6, 116.8, 110.8, 110.1, 46.9, 26.6. MS: m / z 536 [M &lt; + &gt;]. Anal. Calcd for C ₃₅ H ₂₄ N ₂ O ₂ S: C, 78.33; H, 4.51. Found: C, 78.05; H, 4.44.

VIII) 2-cyano-3- (5- (5- (9- (9,9-dimethylfluoren-2-yl) carbazol-6-yl) thiophen-2-yl) -thiophen-2 -Yl) acrylic acid (compound 1a-2)

The same process as in step VII) was carried out to obtain the title compound as a red solid (yield 86%).

Mp: 258 ° C. _{1H NMR (DMSO- d 6):} δ 8.66 (s, 1H), 8.40 (d, 1H, J = 8.1 Hz), 8.11 (d, 1H, J = 7.8 Hz), 8.07 (s, 1H), 7.94 ( d, 1H, J = 8.1 Hz), 7.88 (s, 1H), 7.81 (d, 1H, J = 7.8 Hz), 7.66 (d, 1H, J = 3.9 Hz), 7.61 (m, 3H), 7.53 ( d, 1H, J = 3.9 Hz), 7.49-7.32 (m, 7H), 1.53 (s, 6H). 13C {1H} NMR (DMSO- d 6): δ 162.8, 155.4, 154.5, 153.7, 145.2, 141.2, 140.8, 140.0, 139.9, 138.1, 137.8, 136.5, 136.2, 135.7, 135.6, 133.7, 127.8, 127.3, 127.1 , 126.9, 125.9, 125.5, 125.4, 124.2, 124.0, 123.4, 122.9, 122.7, 121.6, 121.3, 121.11, 120.5, 119.5, 117.6, 110.5, 110.0, 49.9, 26.7. MS: m / z 618 [M &lt; + &gt;]. Anal. Calcd for C ₃₉ H ₂₆ N ₂ O ₂ S ₂ : C, 75.70; H, 4.24. Found: C, 75.42; H, 4.13.

IX) 2- (5-((5- (9- (9,9-dimethylfluoren-2-yl) carbazol-6-yl) thiophen-2-yl) methylene) -4-oxo-2- Thioxothiazolidin-3-yl) acetic acid (Compound 1b-1)

Compound 5 (n = 1) (0.3 g, 0.64 mmol) prepared in step V) above was dissolved in acetic acid (30 mL), and with stirring, rhodanine-3-acetic acid (0.13 g, 0.67 mmol) and ammonium acetate (0.02 g, 0.26 mmol) was added. The mixture was then heated to 120 ° C. and reacted for 2 hours. After cooling the reaction solution to room temperature, the solid was collected by filtration and washed with water. The solid was dried in air and the crude product was subjected to silica gel chromatography (eluent CH ₂ Cl ₂ : MeOH = 10: 1) to afford the title compound as a black solid (yield 74%).

Mp: 261 ° C. _{1H NMR (DMSO- d 6):} δ 8.78 (s, 1H), 8.45 (d, 1H, J = 7.5 Hz), 8.13 (d, 1H, J = 8.1 Hz), 8.06 (s, 1H), 7.95 ( d, 1H, J = 8.1 Hz), 7.92 (d, 1H, J = 7.5 Hz), 7.90 (s, 1H), 7.82 (m, 2H), 7.62 (d, 1H, J = 8.1 Hz), 7.61 ( d, 1H, J = 8.4 Hz), 7.52-7.33 (m, 6H), 4.34 (s, 2H), 1.54 (s, 6H). 13C {1H} NMR (DMSO- d ₆ ): δ 191.9, 175.2, 167.1, 166.6, 155.4, 153.7, 153.1, 140.9, 140.6, 138.2, 137.8, 137.6, 135.6, 135.4, 127.8, 127.3, 127.0, 125.5, 124.9 , 124.6, 124.5, 123.5, 122.9, 122.6, 121.6, 121.3, 121.2, 120.6, 120.5, 119.1, 118.2, 110.6, 110.1, 46.9, 26.7, 23.5. MS: m / z 642 [M &lt; + &gt;]. Anal. Calcd for C ₄₁ H ₂₈ N ₂ O ₃ S ₄ : C, 67.93; H, 3.89. Found: C, 68.90; H, 3.80.

X) 2- (5-((5- (5- (9- (9,9-dimethylfluoren-2-yl) carbazol-6-yl) thiophen-2-yl) thiophen-2-yl ) Methylene) -4-oxo-2-thioxothiazolidin-3-yl) acetic acid (compound 1b-2)

The same process as in step IX) was carried out to obtain the title compound as a black solid (yield 71%).

Mp: 305 ° C. _{1H NMR (DMSO- d 6):} δ 8.64 (s, 1H), 8.38 (d, 1H, J = 7.8 Hz), 8.09 (d, 1H, J = 8.1 Hz), 8.02 (s, 1H), 7.94 ( d, 1H, J = 8.1 Hz), 7.87 (s, 1H), 7.79 (d, 1H, J = 8.7 Hz), 7.73 (d, 1H, J = 3.9 Hz), 7.53 (d, 1H, J = 3.9 Hz), 7.63-7.30 (m, 10H), 4.37 (s, 2H), 1.52 (s, 6H). 13C {1H} NMR (DMSO- d ₆ ): δ 191.6, 189.5, 179.1, 176.1, 171.5, 166.5, 160.0, 156.4, 155.4, 153.7, 145.8, 144.6, 143.7, 140.9, 140.1, 138.1, 137.8, 135.8, 135.5 , 133.3, 125.5, 125.3, 124.2, 123.9, 123.4, 122.9, 122.6, 122.5, 121.6, 121.2, 120.5, 119.6, 115.1, 112.4, 110.5, 110.3, 105.1, 46.9, 26.6, 23.8. MS: m / z 724 [M &lt; + &gt;]. Anal. Calcd for C ₃₇ H ₂₆ N ₂ 0 ₃ S ₃ : C, 69.13; H, 4.08. Found: C, 69.01; H, 4.02.

XI) 9- (4- (2,2-diphenylvinyl) phenyl) -3- (thiophen-2-yl) carbazole (Compound 6)

The same process as in step III) above gave the title compound as a white solid (yield 68%).

Mp: 214 ° C. 1 H NMR (CDCl ₃ ): δ 8.45 (s, 1H), 8.24 (d, 1H, J = 7.5 Hz), 7.74 (d, 1H, J = 8.4 Hz), 7.54-7.32 (m, 20H), 7.19 ( dd, 1H, J = 5.1, 3.9 Hz), 7.15 (s, 1H). 13C {1H} NMR (CDCl ₃ ): δ 145.9, 145.3, 143.9, 143.2, 142.5, 141.5, 141.0, 140.2, 137.2, 135.5, 131.2, 130.4, 130.1, 129.0, 128.5, 128.2, 127.8, 127.5, 127.0, 126.7 , 126.4, 125.8, 125.4, 124.5, 123.7, 123.6, 123.2, 122.3, 120.6, 120.1, 119.6, 118.0, 111.4, 110.8. MS: m / z 503 [M &lt; + &gt;]. Anal. Calcd for C ₃₆ H ₂₅ NS: C, 85.85; H, 5.00. Found: C, 85.64; H, 4.86.

XII) 5- (9- (4- (2,2-diphenylvinyl) phenyl) carbazol-6-yl) thiophene-2-carbaldehyde (Compound 7)

The same process as in step V) was carried out to obtain the title compound as a yellow solid (yield 82%).

Mp: 222 ° C. 1 H NMR (CDCl ₃ ): δ 9.89 (s, 1H), 8.41 (s, 1H), 8.15 (d, 1H, J = 7.5 Hz), 7.75 (d, 1H, J = 3.6 Hz), 7.69 (d, 1H, J = 8.4 Hz), 7.44 (d, 1H, J = 3.9 Hz), 7.42-7.27 (m, 17H), 7.25 (d, 1H, J = 3.9 Hz), 7.08 (s, 1H). 13C {1H} NMR (CDCl ₃ ): δ 182.7, 156.1, 143.9, 143.2, 141.6, 141.5, 141.4, 141.0, 140.2, 139.2, 137.9, 137.1, 136.7, 135.5, 131.1, 130.4, 129.0, 128.5, 128.0, 127.9 , 127.8, 127.0, 126.8, 126.4, 125.9, 125.3, 124.7, 124.5, 124.1, 123.2, 120.8, 120.6, 118.5, 110.6, 110.4. MS: m / z 531 [M &lt; + &gt;]. Anal. Calcd for C ₃₇ H ₂₅ NOS: C, 83.59; H, 4.74. Found: C, 83.36; H, 4.66.

XIII) 2-cyano-3- (5- (9- (4- (2,2-diphenylvinyl) phenyl) carbazol-6-yl) thiophen-2-yl) -acrylic acid (Compound 1c)

The same process as in step VII) was carried out to obtain the title compound as a red solid (yield 78%).

Mp: 255 ° C. _{1H NMR (DMSO- d 6):} δ 8.62 (s, 1H), 8.34 (d, 1H, J = 7.5 Hz), 8.13 (s, 1H), 7.75 (d, 1H, J = 7.5 Hz), 7.73 ( d, 1H, J = 3.9 Hz), 7.66 (d, 1H, J = 3.9 Hz), 7.51-7.24 (m, 19H). 13C {1H} NMR (DMSO- d 6): δ 163.9, 152.5, 150.3, 149.8, 145.9, 143.7, 142.6, 142.4, 140.8, 140.6, 140.1, 139.8, 136.6, 136.4, 135.8, 135.3, 134.9, 130.9, 129.7 , 129.2, 128.5, 127.9, 127.8, 127.2, 126.9, 126.8, 126.1, 125.4, 124.6, 123.5, 122.6, 121.1, 120.6, 119.3, 118.0, 110.5, 109.9, 108.3. MS: m / z 598 [M &lt; + &gt;]. Anal. Calcd for C ₄₀ H ₂₆ N ₂ O ₂ S: C, 80.24; H, 4.38. Found: C, 79.94; H, 4.27.

XIV) 9- (9,9-dimethylfluoren-2-yl) -3- (5- (2- (thiophen-2-yl) vinyl) thiophen-2-yl) carbazole (Compound 8)

(2-thienylmethyl) triphenylphosphonium bromide (0.65 g, 1.48 mmol) was suspended in THF (20 mL) at room temperature under N ₂ atmosphere, and then ^t BuOK (0.17 g, 1.49 mmol) was added thereto. After cooling the mixed solution to 0 ° C., a solution of Compound 5 (n = 1) (0.7 g, 1.48 mmol) in THF was added dropwise. The mixture was stirred at 0 ° C. for 1 h and then further at rt for 8 h. The reaction solution was diluted with CH ₂ Cl ₂ , washed twice with water, and dried over anhydrous sodium sulfate. After removing the solvent under reduced pressure, the obtained solid was subjected to silica gel chromatography (developing agent CH ₂ Cl ₂ : Hx = 1: 3) to give the title compound as a white solid (yield 73%).

Mp: 238 ° C. 1 H NMR (CDCl ₃ ): δ 8.44 (s, 1H), 8.26 (d, 1H, J = 7.8 Hz), 7.95 (d, 1H, J = 8.4 Hz), 7.84 (d, 1H, J = 7.2 Hz) , 7.73 (d, 1H, J = 8.7 Hz), 7.68 (s, 1H), 7.57-7.33 (m, 9H), 7.29 (d, 1H, J = 3.9 Hz), 7.23 (d, 1H, J = 15.9 Hz), 7.22 (d, 1H, J = 5.1 Hz), 7.13 (d, 1H, J = 3.9 Hz), 7.11 (d, 1H, J = 15.9 Hz), 7.05 (dd, 1H, J = 3.9, 5.1 Hz), 1.62 (s, 6 H). 13C {1H} NMR (CDCl ₃ ): δ 155.7, 154.0, 144.5, 142.9, 141.7, 141.0, 140.8, 138.9, 138.6, 136.5, 128.3, 127.9, 127.5, 127.0, 126.8, 126.6, 126.3, 126.1, 125.9, 124.5 , 124.4, 124.1, 123.5, 122.9, 122.5, 122.0, 121.5, 121.4, 121.0, 120.8, 120.5, 117.7, 110.5, 110.3, 47.4, 27.4. MS: m / z 549 [M &lt; + &gt;]. Anal. Calcd for C ₃₇ H ₂₇ NS ₂ : C, 80.84; H, 4.95. Found: C, 80.59; H, 4.85.

XV) 5- (2- (5- (9- (9,9-dimethylfluoren-2-yl) carbazol-6-yl) thiophen-2-yl) vinyl) thiophene-2-carbaldehyde ( Compound 9)

The same process as in step V) was carried out to obtain the title compound as a yellow solid (yield 73%).

Mp: 247 ° C. 1 H NMR (CDCl ₃ ): δ 9.82 (s, 1H), 8.38 (s, 1H), 8.20 (d, 1H, J = 7.5 Hz), 7.92 (d, 1H, J = 8.1 Hz), 7.81 (d, 1H, J = 7.8 Hz), 7.67 (d, 1H, J = 8.7 Hz), 7.63 (s, 1H), 7.60 (d, 1H, J = 3.9 Hz), 7.53-7.33 (m, 8H), 7.28 ( d, 1H, J = 3.9 Hz), 7.23 (d, 1H, J = 15.9 Hz), 7.11 (d, 1H, J = 3.9 Hz), 7.07 (d, 1H, J = 3.3 Hz), 6.99 (d, 1H, J = 15.9 Hz), 1.58 (s, 6H). 13C {1H} NMR (CDCl ₃ ): δ 182.4, 155.7, 154.0, 152.4, 146.7, 141.7, 141.3, 141.0, 139.7, 138.9, 138.4, 137.4, 136.3, 129.9, 127.8, 127.4, 126.6, 126.2, 125.9, 124.4 , 124.0, 123.3, 123.2, 123.0, 122.9, 121.4, 121.3, 120.7, 120.6, 120.5, 120.3, 119.4, 117.8, 110.5, 110.3, 47.3, 27.2. MS: m / z 577 [M &lt; + &gt;]. Anal. Calcd for C ₃₈ H ₂₇ NOS ₂ : C, 79.00; H, 4.71. Found: C, 78.78; H, 4.57.

XVI) 2-cyano-3- (5- (2- (5- (9- (9,9-dimethylfluoren-2-yl) carbazol-6-yl) thiophen-2-yl) vinyl) Thiophen-2-yl) acrylic acid (Compound 1d)

The same process as in step X) above gave the title compound as a red solid (yield 85%).

Mp: 284 ° C. _{1H NMR (DMSO- d 6):} δ 8.61 (s, 1H), 8.36 (d, 1H, J = 7.8 Hz), 8.12 (d, 1H, J = 8.1 Hz), 8.07 (s, 1H), 7.95 ( d, 1H, J = 7.8 Hz), 7.88 (s, 1H), 7.77 (t, 1H, J = 8.4 Hz), 7.68 (d, 1H, J = 7.5 Hz), 7.63-7.31 (m, 12H), 7.19 (d, 1 H, J = 15.9 Hz), 1.54 (s, 6 H). 13C {1H} NMR (DMSO- d ₆ ): δ 163.3, 162.6, 161.4, 159.4, 155.3, 153.7, 149.7, 146.9, 144.6, 141.2, 140.8, 140.0, 139.8, 138.1, 137.7, 135.7, 135.6, 132.2, 129.9 , 127.7, 127.2, 126.8, 125.8, 125.5, 124.2, 123.9, 123.6, 123.3, 122.8, 122.6, 121.5, 121.2, 120.9, 120.4, 119.2, 117.3, 110.5, 109.9, 46.8, 26.6. MS: m / z 644 [M &lt; + &gt;]. Anal. Calcd for C ₄₁ H ₂₈ N ₂ O ₂ S ₂ : C, 76.37; H, 4.38. Found: C, 76.14; H, 4.21.

Example 2 Fabrication of Dye-Sensitized Solar Cell

In order to evaluate the current-voltage characteristics of the dye compound, a solar cell was manufactured using a 13 + 10 μm TiO ₂ transparent layer. The washed FTO (Pilkington, 8 μsq ⁻¹ ) glass substrate was impregnated in 40 mM TiCl ₄ aqueous solution. A TiO ₂ paste (Solaronix, 13 nm anatase) was screen printed to produce a 13 μm thick first TiO ₂ layer, and a _second paste of 10 μm thick TiO ₂ scattering layer (CCIC, HWP-400) was used for light scattering. Prepared. This TiO ₂ electrode was prepared by the solution of each of the dye compounds 1a-1, 1a-2, 1b-1, 1b-2, 1c and 1d of the present invention prepared in steps VII) to X), XIII) and XVI). 0.3 mM dye in 3a, 7a-dihydroxy-5b-cholic acid-containing ethanol) and left at room temperature for 18 hours. A counter electrode was prepared by coating a H ₂ PtCl ₆ solution (2 mg Pt in 1 mL ethanol) on an FTO substrate. Then, an electrolyte in which 0.6 M 3-hexyl-1,2-dimethylimidazolium iodine, 0.04 MI ₂ , 0.025 M LiI, 0.05 M guanidium thiocyanate and 0.28 M tert -butylpyridine was dissolved in acetonitrile was obtained. Injected into. The photovoltaic performance of the solar cell was measured using a 1000 W xenon light source. The IPCE spectrum of the solar cell was measured using an IPCE measurement system (PV measurement).

Example 3 Measurement of Physical Properties of Prepared Dye and Dye-Sensitized Solar Cell

Absorption spectra in ethanol of the dye compounds 1a-1, 1a-2, 1b-1, 1b-2, 1c and 1d of the dye compounds of the present invention prepared in steps VII) to X), XIII) and XVI), respectively ) And the emission spectrum (solid line) and the absorption spectrum (solid line) when supported on the TiO ₂ layer are shown in FIG. 1 ((a): 1a-1, (b): 1a-2, (c): 1b -1, (d): 1b-2, (e): 1c, (f): 1d).

From the graph of FIG. 1, it can be seen that as the π-binding system increases, the absorption spectrum shifts toward the red side. In addition, it can be seen from the graph of FIG. 1 that the N-substituted carbazole unit inhibits aggregation through molecular adhesion to induce a non-planar structure, and the larger the bound dye, the less the inhibition of aggregation.

In addition, the geometries (molecular orbitals of HOMO and LUMO, calculated by TD-DFT for B3LYP / 3-21G) of compounds 1a-1, 1a-2, 1b-1, 1b-2, 1c, and 1d, respectively, are shown in FIG. 2. Shown in From this, it can be seen that HOMO-LUMO excitation shifts the electron distribution from the carbazole unit to the cyanoacrylic acid group, and photoinduced electron transport from the dye to the TiO ₂ electrode can be efficiently performed by the HOMO-LUMO transition. It can be seen.

Optical and electrochemical performances of the dye compounds 1a-1, 1a-2, 1b-1, 1b-2, 1c, and 1d of the present invention are shown in Table 1 below, and solar cells prepared using the respective dye compounds. The photoelectrochemical characteristics and the IPCE spectrum of the are shown in Table 2 and FIG.

In Table 1, ε represents an absorption coefficient, E _ox represents an oxidation potential, and E _{0 -0} represents a voltage at an intersection point of an absorption and emission spectrum. In addition, a is the absorption spectrum is measured in the ethanol solution, b is the absorption spectrum is measured on the TiO ₂ film, c is the emission spectrum is measured in the ethanol solution, d is the redox potential of the dye on TiO ₂ 50 mV s ^-1 at a scan rate of ^{(vs. Fc / Fc +) 0.1M} (n -C 4 H 9) is measured in CH ₃ CN using the ₄ n-PF _6, e is extinction of ethanol from the e _0-0 And from the intersection of the emission spectra, f means that E _LUMO is calculated by E _ox -E _0-0 .

In Table 2, N719 is a ruthenium-based catalyst used in a conventional dye-sensitized solar cell and has a structure as follows.

In Table 2, J _sc represents a short-circuit photocurrent density, V _oc represents an open circuit photovoltage, ff represents a fill factor, and η represents an overall optical conversion efficiency. . At this time, the performance of the fuel-sensitized solar cell was measured to 0.18cm ² working area.

IPCE graph of the solar cell of Figure 3 (1a-1: bar line, 1a-2: dashed line, 1b-1: bar line-dotted line, 1b-2: bar line-dotted line-dotted line, 1c: short bar line, 1d: The short dashed line, N719: solid line) shows that the IPCE maximums of the compounds 1a-1 and 1a-2 are particularly high and the conversion efficiency is also excellent.

The novel N-arylcarbazole moiety-containing dye of the present invention exhibits improved molar absorption coefficient, J _sc (short circuit photocurrent density) and photoelectric conversion efficiency than conventional metal complex dyes, which can greatly improve the efficiency of solar cells. As a result, purification can be performed without using an expensive column, thereby significantly lowering the cost of dye synthesis.

Claims (11)

N-arylcarbazole dyes represented by Formula 1 below: [Formula 1]

Where X is 9,9-dimethylfluorenyl or 4- (2,2-diphenylvinyl) phenyl, Y is a cyanoacrylic acid residue or a rhodanine-3-acetic acid residue, n is an integer from 1 to 5, optionally two or more thiophene units may be linked to a vinyl group. The method of claim 1, N-arylcarbazole-based dye, characterized in that the dye is represented by the formula 1a-1, 1a-2, 1b-1, 1b-2, 1c or 1d: [Formula 1a-1]

[Formula 1a-2]

[Formula 1b-1]

[Formula 1b-2]

[Formula 1c]

&Lt; RTI ID = 0.0 &

(1) 3-iodocarbazole is subjected to still coupling reaction with a compound of Formula 2 to prepare a compound of Formula 3, (2) preparing a compound of formula 4 by reacting a compound of formula 3 with 2-iodo-9,9-dimethylfluorene and Ullmann; (3) preparing a compound of formula 5 by lithiation of the compound of formula 4 with n-butyllithium and subsequently cooling with dimethylformamide (DMF); (3) reacting the compound of formula 5 with cyanoacetic acid in the presence of piperidine in CH ₃ CN or reacting the compound of formula 5 with rhodanine-3-acetic acid and ammonium acetate in acetic acid Method for preparing an N-arylcarbazole dye represented by Formula 1a or 1b: [Formula 1a]

[Chemical Formula 1b]

[Formula 2]

(3)

[Formula 4]

[Chemical Formula 5]

Wherein n is an integer from 1 to 5, optionally two or more thiophene units may be linked to a vinyl group. (1) 3-iodocarbazole is subjected to still coupling reaction with a compound of Formula 2 to prepare a compound of Formula 3, (2) a compound of Chemical Formula 3 is prepared by coupling a compound of Chemical Formula 3 with 1- (2- (4-bromophenyl) -1-phenylvinyl) benzene and Ullmann; (3) formally compounding the compound of formula 6 with n-butyllithium to prepare a compound of formula 7, (3) reacting the compound of formula 7 with cyanoacetic acid in the presence of piperidine in CH ₃ CN Method for preparing an N-arylcarbazole dye represented by the following Chemical Formula 1c: [Formula 1c]

[Formula 2]

(3)

[Formula 6]

[Formula 7]

Wherein n is 1. (1) 3-iodocarbazole is subjected to still coupling reaction with a compound of Formula 2 to prepare a compound of Formula 3, (2) preparing a compound of formula 4 by reacting a compound of formula 3 with 2-iodo-9,9-dimethylfluorene and Ullmann; (3) Lithium-substituted compound of Formula 4 with n-butyllithium and subsequently cooled with dimethylformamide to prepare a compound of Formula 5 (4) A compound of formula 8 is prepared by coupling a compound of formula 5 with (2-thienylmethyl) triphenylphosphinium bromide and Honor-Emmons-Wittig. (5) preparing a compound of formula 9 by formylating a compound of formula 8 with n-butyllithium, (6) reacting a compound of formula 9 with cyanoacetic acid in the presence of piperidine in CH ₃ CN Method for preparing an N-arylcarbazole dye represented by Chemical Formula 1d: &Lt; RTI ID = 0.0 &

[Formula 2]

(3)

[Formula 4]

[Chemical Formula 5]

[Formula 8]

[Formula 9]

Wherein n is 1. A dye-sensitized photoelectric conversion device comprising oxide semiconductor fine particles carrying the N-arylcarbazole dye of claim 1. The method of claim 6, A dye-sensitized photoelectric conversion device characterized in that an N-arylcarbazole-based dye is supported on the oxide semiconductor fine particles in the presence of an inclusion compound. The method of claim 6, Dye-sensitized photoelectric conversion device, characterized in that the oxide semiconductor fine particles contain titanium dioxide as an essential component. The method of claim 6, Dye-sensitized photoelectric conversion device, characterized in that the oxide semiconductor fine particles have an average particle diameter of 1 to 500 nm. A dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion device of claim 6 as an electrode. The method of claim 10, Wherein the dye-sensitized solar cell, coating a titanium oxide paste on a conductive transparent substrate, baking the paste-coated substrate to form a titanium oxide thin film, the dye represented by the formula (1) is dissolved in a substrate formed with a titanium oxide thin film Impregnating the mixed solution to form a titanium oxide film electrode on which dye is adsorbed, and providing a second glass substrate having a counter electrode formed thereon, a hole penetrating through the second glass substrate and the counter electrode. Forming a thermoplastic polymer film between the counter electrode and the titanium oxide film electrode to which the dye is adsorbed, and performing a heat compression process to bond the counter electrode and the titanium oxide film electrode to each other; Injecting an electrolyte into the thermoplastic polymer film between the pole and the titanium oxide film electrode, and the thermoplastic polymer The dye-sensitized solar cell, characterized in that is produced through the step of sealing.

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